WO2000018504A1 - Article photocatalyseur, article protege contre l'encrassement et le voilement, et procede de production d'un article protege contre l'encrassement et le voilement - Google Patents

Article photocatalyseur, article protege contre l'encrassement et le voilement, et procede de production d'un article protege contre l'encrassement et le voilement Download PDF

Info

Publication number
WO2000018504A1
WO2000018504A1 PCT/JP1999/005304 JP9905304W WO0018504A1 WO 2000018504 A1 WO2000018504 A1 WO 2000018504A1 JP 9905304 W JP9905304 W JP 9905304W WO 0018504 A1 WO0018504 A1 WO 0018504A1
Authority
WO
WIPO (PCT)
Prior art keywords
antifogging
article according
group
oxide
compound
Prior art date
Application number
PCT/JP1999/005304
Other languages
English (en)
Japanese (ja)
Inventor
Kazuhiro Doushita
Hiroyuki Inomata
Original Assignee
Nippon Sheet Glass Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Sheet Glass Co., Ltd. filed Critical Nippon Sheet Glass Co., Ltd.
Priority to DE69930399T priority Critical patent/DE69930399T2/de
Priority to EP99944879A priority patent/EP1066878B1/fr
Priority to KR1020007004650A priority patent/KR20010031599A/ko
Publication of WO2000018504A1 publication Critical patent/WO2000018504A1/fr
Priority to US09/577,299 priority patent/US6576344B1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/45—Inorganic continuous phases
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials
    • C03C2217/477—Titanium oxide
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/71—Photocatalytic coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less

Definitions

  • the present invention relates to a photocatalyst article, an antifogging and antifouling article, and a method for producing the antifogging and antifouling article.
  • the present invention relates to an anti-fogging and anti-fouling article having a anti-fogging film or an anti-fouling film formed on the surface of a substrate such as glass, ceramics, plastic or metal, a method for producing the same, and a composition for forming these articles.
  • a substrate such as glass, ceramics, plastic or metal
  • Suitable for articles such as film sheets and showcases has good anti-fogging or anti-fouling performance over a long period of time, and particularly exhibits anti-fogging and anti-fouling performance by weak ultraviolet light or visible light, and a method for producing the same and a method for producing the same.
  • Composition Suitable for articles such as film sheets and showcases, has good anti-fogging or anti-fouling performance over a long period of time, and particularly exhibits anti-fogging and anti-fouling performance by weak ultraviolet light or visible light, and a method for producing the same and a method for producing the same. Composition. Background art
  • the photocatalytic activity of titanium oxide is cited as one important factor that determines the antifogging and antifouling performance.
  • a method of improving the photocatalytic activity of titanium oxide a method of supporting a noble metal on titanium oxide (for example, Catalyst, Vol. 19, No. 5, 334-350 (1977)), a method of supporting a vanadium compound on titanium oxide (For example, JP-A-7-275704), a method of dissolving niobium in titanium oxide (for example, JP-A-9-267307), a method of doping titanium oxide with fluorine ( For example, International Publication WO98 / 05413) is mentioned.
  • a small amount of a dopant selected from the group consisting of vanadium, chromium, manganese, iron, cobalt, nickel and copper is added to titanium oxide.
  • a metal ion selected from the group consisting of chromium, vanadium, copper, iron, magnesium, silver, palladium, nickel, manganese and platinum is added to the titanium oxide crystal.
  • a method of injecting a small amount Japanese Patent Publication No. 9-262642.
  • Method 2 is an effective means for some applications, but cannot be applied to glass that requires relatively large mechanical strength, such as automobiles and buildings.
  • Method 3 was devised in order to achieve both anti-fog performance and mechanical strength, but both have limitations in terms of performance. Further, there is also a problem that the antifogging performance is significantly reduced once the stain is attached.
  • Method 4 has features that cannot be realized by other methods in principle.However, since the intensity of ultraviolet light inside vehicles and buildings is very weak, it can be put to practical use. Such anti-fog articles have not been obtained so far. In addition, antifouling articles also have a problem that it is difficult to use in places where the intensity of ultraviolet light is weak.
  • composition or article obtained by the above-mentioned conventional technique for the purpose of improving the photocatalytic activity of titanium oxide against ultraviolet light irradiation and developing the photocatalytic activity against visible light irradiation is characterized by the weak ultraviolet light or visible light irradiation. Sufficient antifogging properties are not exhibited and hydrophilicity is not sufficiently improved, so it is hard to say that antifogging and antifouling properties are significantly improved as compared with ordinary titanium oxide.
  • the present invention provides a composition that exhibits excellent antifogging and antifouling properties even in an environment where there is only weak ultraviolet light or visible light, and that maintains good antifogging and antifouling performance over a long period of time.
  • An object of the present invention is to provide an antifogging and antifouling article having excellent antifogging and antifouling performance, which can be used for, for example, window glasses, mirrors, optical parts, and glazing of automobiles and buildings. Disclosure of the invention
  • the present inventors have conducted intensive studies to achieve the above object. As a result, (1) by adding a considerably large amount of a specific metal compound to an oxide semiconductor such as titanium oxide, it is possible to obtain weak ultraviolet light or visible light. (2) Addition of silicon oxide to the composition further improves antifogging and antifouling properties, and (3) Performance is further improved when titanium oxide is fine particles. I found things.
  • the present invention relates to a photocatalyst article containing an oxide semiconductor, wherein Mg (magnesium), Sc (scandium), V (vanadium), Cr (chromium), Mn (manganese), Y (yttrium) ), A compound containing at least one element selected from the group consisting of Nb (niobium), Mo (molybdenum), Ru (ruthenium), W (tungsten), and Re (rhenium), The ratio (A / B) of the number of atoms (A) to the number of atoms (B) of the metal included in the oxide semiconductor is 0.1. It is a photocatalyst article characterized by being contained as follows.
  • the oxide semiconductors T i0 2, ZnO, Sn0 2, SrT i0 3, W0 3, B i 2 0 3, F ⁇ 2 ⁇ 3, I n 2 ⁇ 3, Mo 0 2 such as a metal oxide Semiconductors.
  • titanium oxide (Tio2) having high catalytic activity and excellent physicochemical stability is preferably used.
  • W0 3 or Mo_ ⁇ is used, also the other oxides of W (or Mo) as the compound of is used.
  • the photocatalyst article of the present invention may be in the form of powder, granules, fibers, flakes, films, coatings, plates, or any other shape. If the minimum dimension or film thickness of the photocatalyst article exceeds 500 nm, the photoactive catalysis at the portion beyond that (the depth measured from the surface) is reduced, so the minimum dimension or film thickness of the photocatalyst article is 2 to 200 Onm. It is preferred that Further, this photocatalyst article can be suitably produced by a sol-gel method.
  • the alkali barrier film a film composed of a single component or a multicomponent component selected from the group consisting of silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, and cerium oxide is preferably used.
  • silicon oxide (silica) is preferably a single component or a multicomponent whose main component is silicon oxide, and more preferably a two-component metal oxide of silicon oxide and zirconium oxide.
  • Metal oxides whose main component is silicon oxide have a low refractive index and can be formed without significantly impairing the optical properties of the glass plate. It is preferable that a two-component metal oxide of silicon oxide and zirconium oxide is used. Alkali barrier performance is very high, so that it is more preferable.
  • the content of zirconium oxide is particularly preferably from 1% by weight to 30% by weight. If the content is less than 1% by weight, the effect of improving the ability to cut off the force is not so different from that of silicon oxide alone, and if the content is more than 30% by weight, the effect of improving the ability to cut off the force is no longer improved, and the refractive index increases. However, it is not preferable because the optical property of the glass plate is hardly controlled because the tendency of the reflectance to be improved due to the above becomes strong.
  • the thickness of the barrier film is preferably 5 nm or more and 300 nm or less. If the thickness is less than 5 nm, the effect of blocking the force is not sufficient, and if the thickness is more than 300 nm, interference colors due to the film become remarkable and it becomes difficult to control the optical properties of the glass plate. Not preferred.
  • the alkali barrier film can be formed by a known method.
  • the sol-gel method for example, Yuji Yamamoto, Kanichi Kamiya, Saio Sakuhana, Journal of the Ceramic Society of Japan, 90, 328-333 (1992)
  • the liquid phase precipitation method for example, 5 9 2 10 0, Tokuhei 4 1 1 3 3 3 0 1 No.
  • vacuum film forming method vacuum film forming method (vacuum vapor deposition, sputtering), baking method 'spray coat (for example, JP-A-53-124523, JP-A-56-96749)
  • CVD method for example, JP-A-55-90441) No., JP-A-1-201046, JP-A-5-208849).
  • the photocatalyst film comprises: (1) a compound containing at least one element selected from Mg, Sc, V, Cr, Mn, Y, Nb, Mo, Ru, W, and Re; and
  • titanium oxide is preferably used from the viewpoint of high catalytic activity and excellent physicochemical stability.
  • titanium oxide is preferably used from the viewpoint of high catalytic activity and excellent physicochemical stability.
  • Compounds containing at least one element selected from the group consisting of Mg, Sc, V, Cr, Mn, Y, Nb, Mo, Ru, W, and Re include chlorides, nitrates, sulfates, and salts of each metal. Cetyl acetone compounds, ammonium salts, phosphates, hydroxides, ortho acids, isopoly acids, heteropoly acids, ortho salts, isopoly salts, heteropoly salts, oxides, and the like are used. Of the above elements, V, Nb and Mo are preferably used.
  • the ratio (A / B) of the number of metal atoms (A) to the number of Ti atoms (B) in the compound is 0.20 or more and 2 or less. If the ratio is less than 0.20, the antifogging and antifouling properties will not be exhibited by irradiation with weak ultraviolet light or visible light, and if it is more than 2, the transparency of the thin film will decrease, and the durability will decrease, which is not preferable.
  • This ratio is preferably at least 0.3 in order to shorten the time required for the development of antifogging and antifouling properties by irradiation with weak ultraviolet light or visible light, and to reduce the haze of the film, the ratio is preferably 1 or more. It is preferably at most 0.
  • the ratio (A / B) of the number of metal atoms (A) to the number of Ti atoms (B) in the compound is 0.20 or more and 2 or less, the compound tends to aggregate and exist, and the compound Forms a certain kind of bonding interface with the titanium oxide crystal. At this interface The separation of holes and electrons is promoted by light irradiation, so that even weak UV light becomes hydrophilic.
  • the photocatalyst film in the present invention is produced by using a usual thin film production method.
  • the sol-gel method is preferably applied.
  • Silicon oxide and silica compounds are mixed with a solvent, and if necessary, water, an acid catalyst, a stabilizer and a dispersing agent are added to prepare a coating solution for forming a photocatalytic film on a substrate. I do.
  • Titanium compounds that can be hydrolyzed and polycondensed, titanium tetrachloride and their hydrolysates, and titanium oxide and titanium oxide colloids obtained by heat-treating these compounds as raw materials for titanium oxide fine particles to be present in the film And titanium oxide fine particles are preferably used. Further, it is simple and preferable to use a commercially available liquid in which titanium oxide fine particles are dispersed in a silica binder.
  • Examples of commercially available liquids include “ST-K01” (manufactured by Ishihara Sangyo Co., Ltd., titanium oxide content 8% by weight, silicic acid binder content 2% by weight) and “CA-62” (Taki Chemical Co., Ltd.) Co., Ltd., titanium oxide content 6% by weight, silica binder amount 1.5% by weight).
  • titanium alkoxide for example, titanium methoxide, ethoxide, propoxide, butoxide and the like are preferably used alone or as a mixture.
  • acetylaceton is the above-mentioned organic titanium compound, titanium tetrachloride It is preferable to add twice the molar amount of Ti and the hydrolyzate thereof.
  • the average particle diameter of the titanium oxide fine particles is preferably 2 nm or more and 12 O nm or less. If the average particle size is smaller than 2 nm, the photocatalytic activity is not sufficient and the antifogging and antifouling properties are not very good. On the other hand, if the average particle diameter is larger than 120 nm, the transparency of the thin film is reduced, and the film has a high haze ratio, which is not preferable.
  • the most preferable average particle size is 8 nm or more and 8 O nm or less, and high transparency and high antifogging and antifouling properties are secured in this range.
  • the content of silica preferably present in the photocatalyst film is from 10% by weight to 80% by weight, preferably from 20% by weight to 60% by weight, more preferably from 30% by weight to 50% by weight. It is as follows. If the content is less than 10% by weight, the photocatalytic action itself does not decrease, but the maintenance performance of antifogging and antifouling performance is short, and if it is more than 80% by weight, the content of titanium oxide is reduced, so that antifogging by light irradiation is performed. Antifouling performance is unlikely to occur.
  • silica (silicon oxide) in the film examples include a hydrolyzable / polycondensable organic silicon compound, a chlorosilyl group-containing compound and a hydrolyzate thereof, and silicon oxide, colloidal silica, and silica fine particles obtained by heat-treating the compound. And the like are preferably used.
  • the organosilicon compound and the chlorosilyl group-containing compound may be used alone or in combination.
  • Silica in the film does not need to be present in complete S i0 2 forms, not supported by the difference be present in a form bound alkoxyl group, a hydroxyl group.
  • silicon alkoxides for example, silicon methoxide, ethoxide, propoxide, butoxide and the like are preferably used alone or as a mixture, and a high molecular weight alkyl silicate is preferably used.
  • a high molecular weight alkyl silicate is preferably used.
  • “Ethyl silicate 40” manufactured by Colcoat Co., Ltd. and “MS 56” manufactured by Mitsubishi Chemical Corporation can be used.
  • organic silicon compound hydrolyzate a commercially available alkoxysilane hydrolyzate such as “HAS-10” manufactured by Colcoat Co., Ltd., “Ceramica G-91” manufactured by Nippon Laboratories, Inc. “G-92-6” "Atron NS I-500” manufactured by Nippon Soda Co., Ltd. can be used.
  • chlorosilyl group-containing compound chlorosilyl group (- S i C 1 ⁇ ⁇ 3 ", this Where n is 1, 2, or 3, and X is hydrogen or an alkyl, alkoxy, or acyloxy group having 1 to 10 carbon atoms in the molecule.
  • a compound having at least two chlorines is preferable, and at least two hydrogens in silane S i n H 2n +2 (where n is an integer of 1 to 5) are substituted with chlorine, Chlorosilanes and their condensation polymers, in which other hydrogens are optionally substituted by the above-mentioned alkyl, alkoxy or acyloxy groups, are preferred, such as tetrachlorosilane (silicon tetrachloride, SiCl, trichlorosilane (SiH Ch) Monomethylsilane (SiCH 3 Cl 3 ), dichlorosilane (SiH 2 Cl 2 ), and Cl— (SiCbO) n -SiC k (1 is an integer of 1 to 10).
  • a hydrolyzate of the compound can also be used, and among these, a single compound or a combination of two or more compounds can be used, but the most preferred compound containing a chlorosilyl group is tetrachlorosilane. Very high, forms a dense film by self-condensation or condensation reaction with the substrate surface, and in some cases a film that can sufficiently withstand practical use even when dried at low temperatures (room temperature to 250 ° C) .
  • the solvent of the solution containing the organic silicon compound or the chlorosilyl group-containing compound or the hydrolyzate thereof may be basically any solvent as long as the organic silicon compound or the chlorosilyl group-containing compound or the hydrolyzate thereof is substantially dissolved.
  • Alcohols such as methanol, ethanol, propanol and butanol are most preferred, and the total of the above organosilicon compounds, chlorosilyl group-containing compounds and their hydrolysates is contained at a concentration of 0.001 to 30% by weight. .
  • Water is required for the hydrolysis of the organosilicon compound. This can be any acid or neutral, but to promote the hydrolysis, use water that has been acidified with catalytic hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid, sulfonic acid, etc. Is preferred.
  • the addition amount of the acid is not particularly limited, but is preferably 0.001 to 20 in terms of a molar ratio to the organic silicon compound. When the amount of the added acid is less than 0.001 in molar ratio, the hydrolysis of the organic silicon compound is not sufficiently promoted, and when the amount is more than 2 °, the acidity of the solution becomes too strong, which is preferable in handling. Absent.
  • the upper limit of the amount of the added acid is 2 in a molar ratio to the organosilicon compound. Even if the acid amount increases further, hydrolysis Does not change much. However, the addition of more acid can significantly increase the strength of the film, and in some cases, provide a film that can withstand practical use even at low temperatures (room temperature to 250 ° C).
  • a preferred composition of the coating liquid in which such an increase in photocatalytic film strength is observed is at least one selected from the group consisting of Mg, Sc, V, Cr, Mn, Y, Nb, Mo, Ru, W and Re.
  • the concentration of the compound containing the various elements is 0.0002 to 30% by weight, the concentration of the raw material of the titanium oxide fine particles is 0.0002 to 30% by weight, and the concentration of silicon oxide calculated from the organosilicon compound or its hydrolyzate is , 0.001% by weight or less and 3% by weight or less, acid concentration is 0.001 mol / L or more and 1 mol / L or less, and water content is 0.001% by weight or more and 10% by weight or less. It is. More preferably, the concentration of the metal oxide is 0.01% by weight or more and 0.6% by weight or less, and the acid concentration is 0.01 mol / L or more and 0.3 mol / L or less. The water content is not less than 0.001% by weight and not more than 3% by weight.
  • the acid used at this time is preferably nitric acid or hydrochloric acid, and it is preferable to use an acid having a concentration of at least 0.3 times the water content. That is, when an acid in the form of an aqueous solution is used, it is preferable that the acid be a high-concentration acid having a concentration of 23.1% or more.
  • the concentration of the acid in the ethanol solution is 0.15% by weight or more, provided that the ethanol solution contains, for example, 0.5% by weight of water. Is preferred.
  • the amount of water required for the hydrolysis of the organosilicon compound is preferably 0.1 to 100 in terms of molar ratio with respect to the organosilicon compound. If the amount of water added is less than 0.1 in terms of molar ratio, hydrolysis of the organic metal compound is not sufficiently promoted, and if the amount is greater than 100, the stability of the liquid tends to decrease, which is not preferable.
  • the above organosilicon compound or chlorosilyl group-containing compound is dissolved in a solvent, a catalyst and water are added, and the mixture is hydrolyzed at a predetermined temperature between 10 ° C and the boiling point of the solution for 5 minutes to 2 days.
  • Organic titanium compounds that can be hydrolyzed and polycondensed, titanium tetrachloride and their hydrolysates, and titanium oxide, titanium oxide colloid, and titanium oxide fine particles obtained by heat-treating those compounds, and stabilized as necessary
  • a compound solution containing at least one element selected from the group consisting of Mg, Sc, V, Cr, Mn, Y, Nb, Mo, Ru, W, and Re is added, and A coating liquid for forming a medium film is obtained.
  • a chlorosilyl group-containing compound it is not necessary to add a catalyst and water. Titanium oxide fine particles and compounds containing at least one element selected from Mg, Sc, V, Cr, Mn, Y, Nb, Mo, Ru, W, and Re are May be added before the hydrolysis step. The order in which these are added and mixed is not particularly limited.
  • the above-mentioned commercially available organic silicon compound hydrolyzate solution may be used.
  • the obtained coating liquid may be subsequently diluted with an appropriate solvent according to the coating method.
  • the photocatalyst film-forming coating liquid is applied to a substrate, dried, and, if necessary, subjected to a heat treatment to form a photocatalyst film on the substrate.
  • Examples of the substrate in the present invention include transparent or opaque plate-like bodies, fibers, powders, films, flakes, and other various molded articles made of glass, ceramics, plastic, metal, or the like.
  • the surface of the base material has few hydrophilic groups, for example, a plastic base material or the like is used, the surface is preliminarily treated with plasma or corona discharge to make the surface hydrophilic, or the base material surface is oxygenated. It is preferable to perform the above-mentioned coating after irradiating ultraviolet rays having a wavelength of around 200 to 300 nm in an atmosphere containing the particles to perform a hydrophilicity-imparting treatment.
  • the coating solution for photocatalyst film formation may not be applied uniformly, for example, by repelling it. It can be improved by reforming.
  • cleaning and surface modification methods include degreasing with an organic solvent such as alcohol, acetone, and hexane, cleaning with an alkali or acid, polishing the surface with a polishing agent, and cleaning methods such as ultrasonic cleaning.
  • surface modification methods such as ultraviolet irradiation treatment, ultraviolet ozone treatment, plasma treatment, corona discharge treatment, and heat treatment.
  • the above-mentioned coating method may be performed by using a known technique, and is not particularly limited.
  • a method using an apparatus such as a spinner, a mouth, a sprayer, a sprayer, a forceer, etc.
  • various printing methods such as immersion pulling method (dip coating method), flow coating method (flow coating method), and screen printing, gravure printing, and curved surface printing are used.
  • After forming the photocatalyst film on the substrate drying at a temperature between room temperature and 150 ° C for 1 minute to 2 hours, then densification, improvement of titanium oxide crystallinity, or oxide of added compound If necessary, heat treatment may be performed at a temperature between 350 ° C. and the substrate heat-resistant temperature.
  • the substrate heat resistance temperature is the upper limit temperature at which the properties of the substrate can be substantially maintained.
  • the softening point or the devitrification temperature usually 600 to 700 ° C
  • a plastic substrate such as, for example, the glass transition point, crystallization temperature, decomposition point, and the like can be given.
  • the heat treatment conditions are limited depending on the material of the base material. For example, in the case of a glass substrate, the heat treatment is preferably performed at 350 to 65 ° C. for 5 minutes to 2 hours.
  • the thickness of the photocatalyst film is preferably 2 to 500 nm. If the thickness is less than 2 nm, light cannot be sufficiently absorbed, and the antifogging / fouling / fouling performance deteriorates. If the thickness is more than 500 nm, the photocarrier generated in the film cannot diffuse to the outer surface of the film, so that the photocatalytic activity is reduced, and as a result, the antifogging and antifouling performance is reduced, and interference occurs. Is notably observed, which is not preferable. If the thickness is less than 20 nm, the antifogging / stain resistance when light is not applied tends to decrease.If the thickness is more than 20 nm, the abrasion resistance tends to decrease. Not preferred. A more preferred thickness of the photocatalytic film is from 20 to 200 nm. [Overcoat layer]
  • the antifogging and antifouling performance is further improved.
  • the overcoat layer is at least one metal oxide selected from silicon oxide, aluminum oxide, titanium oxide, zirconia, and cerium oxide, and is preferably a thin film containing silicon oxide at 50% by weight or more. .
  • the coating of the overcoat layer is selected from the group consisting of an organometallic compound of silicon, aluminum, titanium, zirconium, or cerium, a chlorosilyl group-containing compound, and a hydrolyzate thereof, which is capable of hydrolysis and condensation polymerization. It can be formed by applying a liquid containing at least one kind or a liquid obtained by further adding silica fine particles to this liquid on the substrate on which the photocatalytic film is formed.
  • the silica fine particles are preferably used in the form of a solvent dispersion sol (colloid solution).
  • silica sol examples include commercially available water-dispersed sols such as “Snowtex-1 0L”, “Snowtex-1 0", “Snowtex-1 OUP”, and “Snowtex Sue-UP” manufactured by Nissan Chemical Industries, Ltd.
  • Commercially available organic solvent-dispersed silica sols such as “IPA-ST” and “XBA-ST” manufactured by Kogyo Co., Ltd.
  • As the silica fine particles chain fine particles are preferable. By using the chain-shaped fine particles, the overcoat layer has a three-dimensionally intricate uneven shape, so that a surface uneven shape having high antifogging performance and antifogging durability can be formed.
  • chain colloids examples include “Snowtex — OUP” and “Snowtex-1UP”, which are silica sols manufactured by Nissan Chemical Industries, Ltd. These have a diameter of 10 to 20 nm and a diameter of 40 to 3 nm. It has a length of 00 nm.
  • the dispersion solvent of the sily fine particles is not particularly limited as long as the sily fine particles are substantially stably dispersed.
  • a simple substance or a mixture of water, methanol, ethanol, propanol and the like is preferable, and water is more preferable.
  • the water and the lower alcohol are easily mixed with the solution containing the organometallic compound, and can be easily removed by drying during film formation or heat treatment after film formation. Of these, water is most preferred in the manufacturing environment.
  • a dispersing aid may be added.
  • the dispersing aid is not particularly limited, and is generally used as a dispersing aid.
  • electrolytes such as sodium phosphate, sodium hexametanoate, potassium pyrophosphate, aluminum chloride, and iron chloride, and various surface active agents Agents, various organic polymers, silane coupling agents, titanium coupling agents, and the like.
  • the addition amount is usually 0.01 to 5% by weight based on the silica fine particles.
  • the organometallic compound capable of being hydrolyzed and polycondensed together with the silica fine particles or alone in the coating liquid for forming the overcoat layer is basically any compound as long as it undergoes hydrolysis and dehydration condensation. Good, but a metal alkoxide ⁇ metal chelate is preferred.
  • the metal alkoxide examples include silicon, aluminum, zirconium, titanium, and cerium methoxide, ethoxide, propoxide, and butoxide, which are preferably used alone or as a mixture.
  • the metal chelate an acetyl acetonate complex of silicon, aluminum, zirconium, and titanium is preferably used.
  • a high molecular weight type alkyl silicate for example, “Ethyl silicate 40” manufactured by Colcoat Co., Ltd., and “MS56” manufactured by Mitsubishi Chemical Corporation can be used.
  • a hydrolyzate of an alkoxide of silicon a commercially available alkoxysilane hydrolyzate such as “HAS-10” manufactured by Colcoat Co., Ltd., “Ceramica G-91” or “Ceramica G-9” manufactured by Nippon Research Institute Co., Ltd. 2-6 "and” Atron NSI-500 "manufactured by Nippon Soda Co., Ltd. can be used.
  • the chlorosilyl group-containing compound to be contained in the coating solution for forming the overcoat layer together with the silicic acid fine particles or alone is a chlorosilyl group (one SiC 1 victim ⁇ where ⁇ is 1, 2, or 3; X is hydrogen or a compound having at least one alkyl group, alkoxy group, or acyloxy group having 1 to 10 carbon atoms in the molecule. Among them, at least two chlorine atoms A compound having the following formula is preferable: at least two hydrogens in the silane S i n H 2 n +2 (where n is an integer of 1 to 5) are substituted with chlorine, and other hydrogens are optionally substituted.
  • the above alkyl group, Chlorosilanes substituted with alkoxy groups or acyloxy groups, and polycondensates thereof are preferred.
  • tetrachlorosilane silicon tetrachloride, S i CI, trichlorosilane (S i HC 1 3), trichloro port monomethyl silane (S i CHSC l, Jikuroroshi orchid (S iH 2 C l 2) , and CI- (S i C 1 2 0) n -.
  • S i C 1 3 (n can also be used hydrolyzate of 1 to 1 0 integer), and the like the chlorosilyl group-containing compounds, out of these,
  • the most preferred compound containing a chlorosilyl group is tetrachlorosilane.Since the chlorosilyl group is very reactive, it undergoes self-condensation or condensation reaction with the substrate surface. As a result, a film having high abrasion resistance can be formed, and a film that can sufficiently withstand practical use even when dried at a low temperature (room temperature to 250 ° C) may be obtained.
  • the solvent of the solution containing the organometallic compound or the chlorosilyl group-containing compound or the hydrolyzate thereof may be basically any solvent as long as the organic metal compound or the chlorosilyl group-containing compound or the hydrolyzate thereof is substantially dissolved. . Specifically, alcohols such as methanol, ethanol, propanol and butanol are most preferred.
  • the total of the above-mentioned organometallic compounds, chlorosilyl group-containing compounds and their hydrolysates is 0.000001 to 30% by weight. It can be contained at a concentration. Water is required for the hydrolysis of the organometallic compound.
  • This may be acidic or neutral, but in order to promote the hydrolysis, it is preferable to use water that has been made acidic with catalytic hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid, sulfonic acid, etc. .
  • the amount of water required for the hydrolysis of the organometallic compound is preferably 0.1 to 100 in terms of a molar ratio with respect to the organometallic compound. If the amount of water added is less than 0.1 in molar ratio, hydrolysis of the organic metal compound is not sufficiently promoted, and if it is more than 100, the stability of the solution tends to decrease, which is not preferable. .
  • the amount of the acid added is not particularly limited, but is preferably 0.001 to 20 in a molar ratio to the organometallic compound. If the amount of the added acid is less than 0.001 in molar ratio, the promotion of the hydrolysis of the organometallic compound is not sufficient because it is not preferable, and if the amount is more than 20, the acidity of the solution becomes too strong and the handling becomes difficult. Not preferred. From the viewpoint of hydrolysis alone, The upper limit of the amount of the added acid is 2 in a molar ratio to the organometallic compound. Even if the amount of acid is further increased, the degree of progress of hydrolysis does not change much.
  • the preferred composition of the coating liquid in which such an increase in the film strength of the overcoat layer is recognized is that the concentration of the metal oxide calculated from the organometallic compound or the hydrolyzate thereof is 0.00001% by weight or more. 0.3% by weight or less, the acid concentration is 0.0001 mol / L or more and 1 mol / L or less, and the water content is 0.001% by weight or more and 10% by weight or less.
  • the concentration of the metal oxide is not less than 0.001% by weight and not more than 0.1% by weight, and the concentration of the acid is not less than 0.01 mol / L and not more than 0.3 mol / L.
  • the water content is not less than 0.001% by weight and not more than 3% by weight.
  • the acid used at this time is preferably nitric acid or hydrochloric acid, and it is preferable to use an acid having a concentration of at least 0.3 times the water content. That is, when an acid in the form of an aqueous solution is used, it is preferable that the acid be a high-concentration acid having a concentration of 23.1% or more.
  • the concentration of the acid in the ethanol solution is 0.15% by weight or more, provided that the ethanol solution contains, for example, 0.5% by weight of water. Is preferred.
  • the above-mentioned compound having a silyl group it is not always necessary to add water or an acid. Even if no additional water or acid is added, hydrolysis proceeds due to the water contained in the solvent or the water in the atmosphere. In addition, hydrochloric acid is liberated in the liquid with the hydrolysis, and the hydrolysis further proceeds. However, additional water or acid can be added.
  • the content of the silica fine particles in the film is too small, the effect of adding the metal oxide fine particles, that is, the obtained antifogging and antifouling performance and antifogging and antifouling durability are not sufficient. Not preferred. Conversely, if the content of the silica fine particles is too large, the metal oxide matrix phase derived from the organometallic compound or the chlorosilyl group-containing compound becomes discontinuous, the film becomes brittle, and the strength of the film tends to decrease. become stronger. At the same time, the obtained antifogging and antifouling performance and antifogging and antifouling durability are saturated and do not substantially improve.
  • the content S of the silica fine particles in the film is preferably 5% by weight or more and 80% by weight or less, more preferably 10% by weight or more and 70% by weight or less, and further preferably 2% by weight or less. 0% by weight or more and 60% by weight or less.
  • the above organometallic compound or chlorosilyl group-containing compound is dissolved in a solvent, a catalyst and water are added, and the mixture is hydrolyzed at a predetermined temperature between 10 ° C and the boiling point of the solution for 5 minutes to 2 days.
  • silica fine particles, silica fine particles and a dispersing aid are added thereto, and if necessary, the mixture is further reacted at a predetermined temperature between 10 ° C and the boiling point of the solution for 5 minutes to 2 days.
  • a coating liquid for forming an overcoat layer is obtained.
  • the metal oxide fine particles may be added before the hydrolysis step. Further, in order to omit the step of hydrolyzing the organometallic compound, the commercially available hydrolyzate of the organometallic compound may be used.
  • the obtained coating liquid may be subsequently diluted with an appropriate solvent according to the coating method.
  • the coating solution for forming an overcoat layer is applied to a substrate on which a photocatalytic film has been formed, dried and, if necessary, heat-treated to form a metal oxide overcoat layer on the substrate.
  • the above-mentioned coating method may be performed by using a known technique, and is not particularly limited.
  • a method using an apparatus such as spin-on-one, roll-on, spray-on, curtain-on, etc. Methods such as dip coating and flow coating are used, and various printing methods such as screen printing, gravure printing, and curved surface printing are used.
  • the substrate is dried at a temperature between room temperature and 150 ° C for 1 minute to 2 hours, and if necessary, at a temperature between 350 ° C and the substrate heat-resistant temperature for 5 minutes. It is preferable to perform heat treatment for 2 hours.
  • Substrate heat resistance temperature is the upper limit temperature at which the properties of the substrate can be substantially maintained
  • glass substrates for example, softening point and devitrification temperature (usually 600 to 700 ° C).
  • plastic substrates for example, glass transition point, crystallization temperature, decomposition point, etc. Is mentioned.
  • the average thickness of the overcoat layer is preferably from 0.1 to 50 nm. If the average thickness is less than 0.1 nm, the effect of improving the antifogging and antifouling performance is not remarkable, and if the average thickness is more than 50 nm, the improvement in hydrophilicity and antifogging properties by light irradiation is difficult to be recognized, which is not preferable. .
  • the overcoat is preferably a porous body.
  • the porous body refers to a thin film having a large number of pores, a thin film having many voids between particles, a thin film having an island shape, and the like, and preferably has a porosity of 1 to 50%.
  • the overcoat layer is porous, in particular, a porous material having a porosity of 1 to 50%, the ability to retain moisture on the surface is increased, and the antifogging and antifouling performance is further improved, which is preferable.
  • the anti-fogging property and the hydrophilic property recovering property when irradiated with light are further improved, and as a result, the anti-fogging and anti-fouling property is improved.
  • the porous overcoat layer is formed by adding at least one organic polymer compound selected from the group consisting of polyethylene glycol, polypropylene glycol, and polyvinyl alcohol to the overcoat-forming coating solution and dissolving them.
  • the obtained liquid is applied and dried on the photocatalyst film-formed substrate, and further heated at 350 to 65 ° C for 5 minutes to 2 hours to decompose the added organic polymer compound. It is obtained by doing.
  • the organic polymer compound is added in an amount of 1% by weight or more and 30% by weight or less based on the total solid content in terms of oxide in the overcoat-forming coating liquid. If the addition amount is less than 1% by weight, the formation of pores is not sufficient and the pore formation operation cannot contribute to the improvement of antifogging and antifouling performance, which is not preferable. On the other hand, if the addition amount is more than 30% by weight, the obtained porous film becomes too brittle, which is also not preferable.
  • Photocatalytic films such as highly active titanium oxide films, have a small contact angle of less than 5 degrees immediately after UV irradiation, and have fairly good initial anti-fog performance. However, since the organic matter is easily adsorbed on the surface, the antifogging performance tends to deteriorate with time due to an increase in the amount of the adsorbed organic matter.
  • a SiO x single molecule equivalent layer (X is 1 to 2) on the surface of the photocatalyst film, thereby effectively adsorbing organic substances while maintaining high photocatalytic activity.
  • a monomolecular equivalent layer of SiOx which is an organic adhesion prevention layer, is achieved by chemically adsorbing the vapor of a silicon compound such as 1,3,5,7-tetramethylcyclotetrasiloxane onto the photocatalyst surface.
  • a liquid containing an organosilicon compound for example, tetraalkoxysilane
  • the decomposition can be carried out suitably.
  • the monomolecular equivalent layer is a substantially monomolecular layer, and refers to a layer of molecules in which 0.5 to 5 molecules are arranged on average in the thickness direction.
  • a polyalkylene oxide group contained in the molecule of the organometallic compound a polyethylene oxide group, a polypropylene oxide group, or the like is mainly used.
  • alkyl group examples include a chain alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, and a decyl group; And a cyclic alkyl group having 3 to 10 carbon atoms, such as a cyclopentyl group and a cyclohexyl group, are mainly used.
  • alkenyl group groups having 1 to 10 carbon atoms such as a vinyl group, an aryl group, a butenyl group, a propenyl group, a hexenyl group, an octenyl group and a cyclohexenyl group are mainly used.
  • a phenyl group, a tolyl group, a xylyl group and the like are mainly used.
  • Organometallic compounds containing these functional groups, for example, polyethylene oxide groups, in the molecule include [alkoxy (polyethyleneoxy) alkyl] trialkoxysilanes and [alkoxy (polyethyleneoxy) alkyl] trichlorosilanes. Examples include silane, and organotitanium compounds such as [alkoxy (polyethyleneoxy) alkyl] trialkoxytitanium.
  • the antifogging and antifouling article prepared using an organosilane containing a polyalkylene oxide group has good antifogging properties and particularly excellent antifogging durability and hydrophilicity retention (that is, antifouling properties). Particularly preferred. As described above, the higher the hydrophilicity maintenance property, the better the antifouling property.
  • the above functional groups are non-reactive or low-reactive, they do not form chemical bonds with dirt components, dirt is not fixed to the surface, and dirt attached to the surface can be easily wiped off. Since it can be removed, even if the antifogging property is lost due to dirt, the antifogging property can be easily restored.
  • the organosilane containing a polyalkylene oxide group is preferably an alkoxysilane or a chlorosilane having an alkoxyl group in the molecule.c
  • the alkoxyl group is easily hydrolyzed, and Since the silane can be chemically bonded to the photocatalyst film and the overcoat layer surface, the product is more anti-fogging and persistent.
  • alkoxysilanes containing a polyethylene oxide group particularly [alkoxy (polyethyleneoxy) alkyl] trialkoxysilanes, for example, [methoxy (polyethyleneoxy) propyl] trimethoxysilane are most preferred. is there.
  • the organosilane or the hydrolyzate thereof contacts the photocatalytic film and the overcoat layer surface.
  • Any method is acceptable.
  • a method of applying the liquid containing the organosilane or its hydrolyzate to the surface of the photocatalyst film and the surface of the overcoat layer (coating method); Or a method of immersing the photocatalyst film-forming article and the photocatalyst film-forming article with an overcoat in a liquid containing the hydrolyzate (liquid-phase chemisorption method); And gas adsorption (gas phase chemical adsorption method).
  • the coating method is the simplest and the lowest cost, and is particularly preferred.
  • the application method described above may be any known technique, and is not particularly limited. Examples thereof include a method using an apparatus such as a spinco, a mouth, a spray, an force, a force, and the like.
  • a method such as a lifting method (dip coating method) or a flow coating method (flow coating method), or a method in which a cloth or paper containing a coating solution is brought into contact with the surface of the photocatalyst uneven film and rubbed with an appropriate force (rubbing method).
  • various printing methods such as screen printing, gravure printing, and curved surface printing.
  • the solvent in which the organosilane is dissolved is not particularly limited, but water, alcohols and ketones are preferably used alone or in combination from the viewpoint of safety, cost and workability.
  • Alcohols include methanol, ethanol, propanol, butanol, and ketones include acetone, methyl ethyl ketone, and getyl ketone.
  • the above-mentioned organosilane is used after being hydrolyzed as required. Add water and, if necessary, an acid catalyst to the organosilane solution, hydrolyze at a certain temperature for a certain time, dilute if necessary and use it for coating.
  • the conditions for the hydrolysis are not particularly limited, but the hydrolysis is preferably performed at a temperature of 20 to 60 ° C. for 3 minutes to 50 hours. If the temperature is lower than 20 ° C or the time is shorter than 3 minutes, the promotion of hydrolysis is not sufficient, and if the temperature is higher than 60 ° C or the time is longer than 50 hours, the hydrolysis is no longer performed. It is not preferable because the effect of promoting decomposition is not improved and the life of the coating solution is shortened.
  • the acid catalyst examples include mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as acetic acid, formic acid, citric acid, and p-toluenesulfonic acid.
  • the amount of the acid to be added is not particularly limited, but is preferably 0.001 to 5 in a molar ratio to the organosilane. If the amount of the added acid is less than 0.001 in a molar ratio, the hydrolysis of the organosilane is promoted. If it is not sufficient, and if the molar ratio is more than 5, the effect of promoting hydrolysis no longer improves, and the acid becomes excessive, which is not preferable.
  • the amount of water to be added for the hydrolysis is not particularly limited, but is preferably 0.1 or more in molar ratio to the organosilane. If the amount of water added is less than 0.1 in terms of molar ratio, the promotion of organosilane hydrolysis is not sufficient, which is not preferable.
  • the concentration of the organosilane solution used for coating is not particularly limited, but 0.001 to 5% by weight is preferably used. If the concentration is lower than 0.001% by weight, the obtained antifogging and antifouling article cannot have a sufficient improvement in the antifogging durability and hydrophilicity maintenance property. It is not economical and unfavorable because the fouling performance does not improve any more.
  • the photocatalyst film and the overcoated photocatalyst film after the application of the organosilane solution are preferably dried or heat-treated at a temperature of 20 to 180 ° C for 3 minutes to 3 hours.
  • the bonding of the organosilane to the surface is strengthened, and the durability, antifogging durability and hydrophilicity retention of the antifogging and antifouling article are improved. If the temperature is lower than 20 ° C. or the time is shorter than 3 minutes, the above effects are not sufficient and are not preferable. If the temperature is higher than 180 ° C, the organosilane may decompose, which is not preferable. Further, if the time is longer than 3 hours, the above effect is no longer improved, and thus it is not preferable from the viewpoint of productivity.
  • organosilane monomolecular equivalent layer is formed on the surface of the photocatalyst film and the overcoat layer, antifogging durability and antifouling property are improved.
  • This organosilane layer is It gradually decomposes due to external factors such as radiation and temperature rise, and eventually becomes a monomolecular equivalent layer of SiOx, maintaining the antifogging durability and antifouling properties.
  • Hydrolysis-condensation polymerization liquid of 96.2 parts by weight of ethanol and ethylsilicone (trade name: HAS-10, manufactured by Colcoat Co., Ltd., silica content: 10% by weight) 3.8 parts by weight were mixed at room temperature for 1 hour By stirring, a coating liquid for forming an alkali-blocking silica film was obtained.
  • the soda lime silicate glass substrate with the alkali-blocking silica film is suspended vertically in an environment of 20 ° C. and 30% RH, and the coating solution for forming a photocatalytic film is allowed to flow from the upper end of the glass substrate.
  • the film was coated on the silica film blocking the flow of heat (flow coating method). Thereafter, by performing a heat treatment at 500 ° C. for 1 hour, a photocatalytic thin film made of silica dispersed with magnesium oxide-added titanium oxide fine particles was formed.
  • the sample thus obtained is referred to as A (glass substrate / silica film / titanium oxide fine particle-dispersed silica thin film with magnesium oxide).
  • Ethanol 463 g hydrolysis polycondensation solution of ethyl silicate (trade name: HAS 110, manufactured by Colcoat Co., Ltd., silica content 10% by weight) 6 g, titania fine particle dispersion (trade name: ST — K01, manufactured by Ishihara Sangyo Co., Ltd., titanium oxide content 8% by weight, inorganic binder content 2% by weight) 10 g, mixed at room temperature for about 1 hour, One ting solution was obtained.
  • HAS 110 hydrolysis polycondensation solution of ethyl silicate
  • silica content 10% by weight silica content 10% by weight
  • titania fine particle dispersion trade name: ST — K01, manufactured by Ishihara Sangyo Co., Ltd., titanium oxide content 8% by weight, inorganic binder content 2% by weight
  • the surface of the soda lime silicate glass substrate provided with the alkali-blocking silica film was coated with the coating solution for forming a photocatalyst film by a flow coating method under the same conditions as in Example 1, and heat-treated under the same conditions as in Example 1.
  • a glass substrate on which a titanium oxide fine particle-dispersed thin film having a thickness of about 70 nm was formed was obtained.
  • the obtained sample is referred to as B (glass substrate / silica film / titanium oxide fine particle dispersed silica thin film).
  • Samples A and B are not exposed to direct sunlight but are indirectly brightened by sunlight, and are kept in a room where people constantly enter and leave, and their surfaces become dirty and the anti-fog property is reduced.
  • the degree of cloudiness when breath was sprayed was evaluated (breath test). That is, the sample immediately after the surface is cleaned does not fog even when breath is blown, but when left indoors, the dirt components in the air are adsorbed on the sample surface and become cloudy by the breath test.
  • the time from the start of indoor standing until the start of fogging was used as an index of antifogging maintenance. It can be said that the larger this value is, the higher the antifogging maintenance property is.
  • the antifogging maintenance of these samples was evaluated according to Table 1 below.
  • UV-cut filter L-42 manufactured by Toshiba Glass Co., Ltd., with a transmittance of 0% at a wavelength of 390 nm or less, 0%, Xenon lamp light (ultraviolet light) over 400 nm, 5% transmittance, 420 nm wavelength, about 50%, 450 nm wavelength, about 80%, visible light above 520 nm, about 90%
  • UV intensity without cut filter 2 mW / cm 2 Measured with UV intensity meter UVR-2 / 110-36 manufactured by Topcon Corporation for 2 hours continuously. Degree (water droplet contact angle recovery amount) was used as an index of anti-fogging recovery.
  • This antifogging recovery property also indicates the catalytic activity performance of the photocatalytic film.
  • the irradiation intensity of 2 mW / cm 2 ultraviolet light corresponds to about 80% of the ultraviolet light intensity included in direct sunlight from outdoor sunlight at 35 ° N in winter, fine weather, and noon. Light that cuts this ultraviolet light
  • the contact angle of a water drop is reduced by (visible light and weak ultraviolet light), it can be said that the sample has a very good anti-fogging recovery property.
  • a contact angle meter (“CA_DT” manufactured by Kyowa Interface Science Co., Ltd.)
  • CA_DT manufactured by Kyowa Interface Science Co., Ltd.
  • Antifouling maintenance was performed by the following outdoor exposure test.
  • Table 4 shows the results of various evaluations of Samples A and B above. It is clear that Sample A (Example 1) has improved antifogging retention, antifogging recovery, and antifouling properties over Sample B (Comparative Example 1).
  • Example 2 Same as in Example 1 except that the surface of the soda lime silicate glass plate (150 X 150 X 3 mm) was polished, washed, and dried in the same manner as in Example 1 without forming an Al film blocking film.
  • the sample thus obtained is referred to as C (glass substrate / silica thin film with scandium compound-added titanium oxide fine particles dispersed therein).
  • Table 4 shows the evaluation results of various antifogging and antifouling performances of Sample C. It is clear that Sample C has better antifogging and antifouling performance than Sample B (Comparative Example 1).
  • alkali barrier film silicon-zirconia thin film
  • solution A 5 parts by weight of zirconium butoxide was added to 1 part by weight of ethyl acetate acetate and stirred at 30 ° C. for 2 hours.
  • solution B 50 parts by weight of tetraethoxysilane, 1000 parts by weight of 2-propanol, 2.5 parts by weight of 1N nitric acid, and 5 parts by weight of water were added, and the mixture was stirred at 30 ° C. for 2 hours.
  • B solution Solution A and solution B were mixed, and the mixture was stirred and cured at 50 ° C for 3 hours and further at 30 ° C for 1 day, to obtain a sol solution for an alkaline barrier film.
  • the surface is polished and washed with a cerium oxide-based abrasive, and then ultrasonically cleaned in pure water.
  • the dried soda lime silicate glass plate (65 mm x 150 mm x 3 mm) is converted to the sol solution for the alkali barrier film. After immersion, the glass plate was pulled up at a speed of 10 cm / min and the sol was applied. Then, it is dried at room temperature for several minutes, and further heat-treated at 500 ° C for 3 hours to obtain a glass plate on which a silica-zirconia thin film (92% by weight of silica, 8% by weight of zirconia) having a thickness of about 30 nm is formed.
  • a silica-zirconia thin film (92% by weight of silica, 8% by weight of zirconia) having a thickness of about 30 nm is formed.
  • Sample D was heat-treated at 500 ° C for 1 hour to form a vanadium oxide-added titanium oxide fine particle-dispersed silica thin film.
  • This sample is designated as D '(glass substrate / silica-zirconia thin film / silica thin film with vanadium oxide-added titanium oxide fine particles dispersed therein).
  • Vanadium oxide added titanium oxide particles dispersed silica thin film of vanadium compound added titanium oxide particles dispersed silica force thin and sample D 5 samples D are each have a thickness of about 60 nm, a silicon oxide 39 wt%, titanium oxide 39 wt%, consists Banaji ⁇ beam compound (V 2 0 5 basis) 22% by weight of the composition was V / T i 0. 5 (atomic ratio).
  • Table 4 shows the results of evaluating various antifogging and antifouling performances of Samples D and D '. It is clear that both samples D and D 'have excellent antifogging and antifouling properties.
  • Manganese oxide-added oxidation was performed in the same manner as in Example 1 except that the heat treatment conditions after coating were changed to 350 ° C for 1 hour on the soda lime silicate glass substrate with a silicon film described in Example 1.
  • the sample thus obtained is designated as F (glass substrate / silica film / manganese oxide-added titanium oxide fine particle-dispersed silica thin film).
  • Table 4 shows the results of evaluating various antifogging and antifouling performances of Sample F. It is clear that it has excellent antifogging and antifouling properties.
  • Titanium oxide fine particles dispersed with titanium oxide are Titanium oxide fine particles dispersed with titanium oxide
  • Example 2 The same method as in Example 1 was applied to the soda lime silicate glass substrate with a silica film described in Example 1.
  • the sample thus obtained is referred to as G (glass substrate / silicone film / titanium oxide-doped titanium oxide fine particle-dispersed silicide film).
  • Table 4 shows the evaluation results of various antifogging and antifouling performances of Sample G.
  • Sample G has remarkably improved antifogging recovery property and good antifogging maintenance property as compared with Sample B (Comparative Example 1), and it is clear that it has excellent antifouling property.
  • the sample thus obtained is referred to as H (glass substrate / silica film / niobium compound-added titanium oxide fine particle-dispersed silica thin film).
  • Table 4 shows the results of evaluating the antifogging and antifouling performance of Sample H. It is clear that it has excellent antifogging and antifouling properties.
  • a molybdenum compound-added titanium oxide thin film was formed in the same manner as in Example 1 except that the heat treatment at 500 ° C was not performed.
  • a glass substrate was obtained.
  • the obtained sample is designated as I (glass substrate / silicone film / molybdenum compound added titanium oxide fine particle dispersed silica thin film).
  • the thickness of the molybdenum compound-added titanium oxide thin film of Sample I was about 40 nm.
  • Table 4 shows the results of various antifogging and antifouling performance evaluations of Sample I. Compared with Sample B (Comparative Example 1), Sample I has remarkably improved antifogging recovery properties and good antifogging maintenance properties, and clearly has excellent antifouling properties.
  • the sample thus obtained is designated as J (glass substrate / silicone film / titanium oxide fine particle-dispersed silica thin film with tungsten oxide).
  • Table 4 shows the results of evaluating the antifogging and antifouling performance of Sample J. Have excellent antifogging and antifouling properties Is evident.
  • magnesium tungstate was added 24.00 0.1N hydrochloric acid and dissolved to obtain a magnesium tungstate added liquid.
  • 90. 85 g of alcohol (trade name: AP-7, manufactured by Nippon Kasei Co., Ltd.) in 0.34 g of tetrachlorosilane and 2.00 g of titania fine particle dispersion (trade name: ST-K01, Ishihara Sangyo) Co., Ltd.) and 6.81 g of the magnesium tungstate-added solution were added at room temperature, and mixed at room temperature for about 1 hour to obtain a coating solution.
  • the sample thus obtained is designated as K (glass substrate / silica film / titanium oxide and silica thin film dispersed with magnesium oxide and titanium oxide fine particles).
  • Table 4 shows the results of evaluating various antifogging and antifouling performances of Sample K. It is clear that it has excellent antifogging and antifouling properties.
  • a SiO 2 monolayer film was formed on the surface of the magnesium oxide-added titanium oxide fine particle-dispersed silicon film of Sample A by the method described below. After setting Sample A in a vacuum desiccator kept at 80 ° C, 200 / L of 1,3,5,7-tetramethylcyclotetrasiloxane (TMCTS) was injected with a syringe. After maintaining for 30 minutes in this state, the temperature was raised to 100 ° C, and unreacted TMCTS was removed by heating for 30 minutes while evacuating the desiccator overnight. By this method, a monomolecular film of TMCTS was formed on the silica film on which the titanium oxide particles containing magnesium oxide were added.
  • TMCTS 1,3,5,7-tetramethylcyclotetrasiloxane
  • the TMCT S film was oxidized by irradiating it with light from a distance of 8 cm for 1 hour using a 500 W high-pressure mercury lamp to convert it to a monomolecular equivalent film of SiOx.
  • sample L glass substrate / silica film with magnesium oxide-added titanium oxide fine particles / Siox single molecule equivalent film
  • Table 4 shows the results of evaluating various antifogging and antifouling performances of Sample L. It is clear that it has excellent antifogging and antifouling properties.
  • a silica overcoat layer was formed on sample D, by the method described below.
  • ethyl silicate trade name: HAS-110, manufactured by Colcoat Co., Ltd.
  • chain silica colloid average diameter about 15 nm, average length about 170 nm, trade name: Snowtex OUP, Nissan Chemical Co., Ltd., solid content 15% by weight
  • sample M glass substrate / silica-zirconia thin film / vanadium oxide added
  • a titanium oxide fine particle-dispersed silica thin film / silica overcoat layer was obtained.
  • the thickness of this silica bar coat layer was about 10 nm.
  • Table 4 shows the results of evaluating the antifogging and antifouling performance of Sample M. It is clear that the formation of the silica bar coat layer has better antifogging and antifouling properties.
  • a silica overcoat layer was further formed on this thin film by the same method as described in Example 12 except that heat treatment at 400 ° C for 1 hour was performed instead of heat treatment at 500 ° C for 1 hour. .
  • the obtained sample is defined as 0 (glass substrate / silicone film / molybdenum oxide-added titanium oxide fine particle thin film / silica overcoat layer).
  • Table 4 shows the evaluation results of various antifogging and antifouling performances of Sample 0. It is clear that Sample 0 has excellent antifogging and antifouling properties.
  • Example 1 94. 99 g of alcohol (trade name: AP-7, manufactured by Nippon Chemical Co., Ltd.) Add 27 g of ruthenium trichloride monohydrate, 0.34 g of tetrachlorosilane and 2.0 g of titania fine particle dispersion (trade name: ST-K01, manufactured by Ishihara Sangyo Co., Ltd.) at room temperature, and add 40 ° The coating liquid was obtained by mixing with C for about 1 hour. In the same manner as in Example 1, a 60 nm-thick ruthenium oxide-doped titanium oxide fine particle-dispersed silica thin film (silicon oxide: 33.3% by weight, titanium oxide) was applied to the soda lime silicate glass substrate having a silicon film described in Example 1.
  • the sample thus obtained is referred to as Q (glass substrate / silicone film / rhenium-doped titanium oxide fine particle-dispersed silica thin film).
  • Table 4 shows the results of evaluating the antifogging and antifouling performance of Sample Q. It is clear that it has excellent antifogging and antifouling properties.
  • the sample thus obtained is referred to as R (glass substrate / silicone film / chromium oxide titanium oxide fine particle dispersed silica thin film).
  • Table 4 shows the results of evaluating the antifogging and antifouling performance of Sample R. It is clear that with Cr doping (addition of a small amount), no improvement in antifogging and antifouling properties is observed.
  • the photocatalyst article of the present invention exhibits high photocatalytic activity under an environment irradiated with weak ultraviolet light or visible light, and the antifogging and stainproof glass article of the present invention has excellent antifogging and antifogging properties. It is clear that it has a fouling performance and its maintainability, and it has good mechanical durability, so that it can be suitably used for automotive, architectural and optical applications. In particular, since it is made hydrophilic by weak ultraviolet light and visible light, it is advantageous for use in places where the amount of ultraviolet rays is small.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Dispersion Chemistry (AREA)
  • Composite Materials (AREA)
  • Catalysts (AREA)

Abstract

Un article photocatalyseur contenant un semi-conducteur à l'oxyde qui contient un composé d'au moins un élément choisi dans le groupe constitué de Mg, Sc, V, Cr, Mn, Y, Nb, Mo, Ru, W et Re, dans certaines proportions, de sorte que le rapport entre (A) le nombre d'atomes de l'élément métallique et (B) les atomes du ou des métaux en tant que composé du semi-conducteur, (A/B), est de 0,20 à 2. Ledit article présente une activité photocatalytique élevée même lorsqu'il est irradié par la lumière visible ou ultraviolette légère, est hautement protégé contre l'encrassement et le voilement et conserve cette propriété de manière satisfaisante sur une longue durée. Ledit article est efficacement protégé contre l'encrassement et le voilement.
PCT/JP1999/005304 1998-09-30 1999-09-28 Article photocatalyseur, article protege contre l'encrassement et le voilement, et procede de production d'un article protege contre l'encrassement et le voilement WO2000018504A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE69930399T DE69930399T2 (de) 1998-09-30 1999-09-28 Photokatalysatorartikel mit verhinderung von verstopfungen und ablagerungen, verfahren zur herstellung des artikels
EP99944879A EP1066878B1 (fr) 1998-09-30 1999-09-28 Article photocatalyseur, article protege contre l'encrassement et le voilement, et procede de production d'un article protege contre l'encrassement et le voilement
KR1020007004650A KR20010031599A (ko) 1998-09-30 1999-09-28 광촉매 물품과 방담방오 물품 및 방담방오 물품의 제조방법
US09/577,299 US6576344B1 (en) 1998-09-30 2000-05-24 Photocatalyst article, anti-fogging, anti-soiling articles, and production method of anti-fogging, anti-soiling articles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10/279058 1998-09-30
JP27905898 1998-09-30

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US09/577,299 Continuation US6576344B1 (en) 1998-09-30 2000-05-24 Photocatalyst article, anti-fogging, anti-soiling articles, and production method of anti-fogging, anti-soiling articles

Publications (1)

Publication Number Publication Date
WO2000018504A1 true WO2000018504A1 (fr) 2000-04-06

Family

ID=17605827

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1999/005304 WO2000018504A1 (fr) 1998-09-30 1999-09-28 Article photocatalyseur, article protege contre l'encrassement et le voilement, et procede de production d'un article protege contre l'encrassement et le voilement

Country Status (5)

Country Link
US (1) US6576344B1 (fr)
EP (1) EP1066878B1 (fr)
KR (1) KR20010031599A (fr)
DE (1) DE69930399T2 (fr)
WO (1) WO2000018504A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003253157A (ja) * 2002-02-28 2003-09-10 Furukawa Co Ltd 貯蔵安定性に優れたチタニア及びチタニア系複合酸化物塗布溶液
JP2005023199A (ja) * 2003-07-02 2005-01-27 Chisso Corp 機能性超薄膜およびその形成方法
JP2005507974A (ja) * 2001-07-13 2005-03-24 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド 可視光応答性の光活性の被膜、被覆物品およびその製法
JP2007508933A (ja) * 2003-10-23 2007-04-12 サン−ゴバン グラス フランス 少なくとも１層の光触媒層と該層のヘテロエピタキシャル成長のための下地層とを備えた基材、特にガラス基材
JP2007106632A (ja) * 2005-10-14 2007-04-26 Kimoto & Co Ltd 新規ヘテロポリ酸塩、それを用いた光触媒、及び光触媒機能性部材
JP2009512573A (ja) * 2005-10-21 2009-03-26 サン−ゴバン グラス フランス 防汚性材料及びその製造方法
JP2009262071A (ja) * 2008-04-25 2009-11-12 National Univ Corp Shizuoka Univ 光触媒、光触媒機能性部材、及び水素の製造方法
JP2010005613A (ja) * 2008-05-26 2010-01-14 Asahi Kasei Chemicals Corp 複合体、機能性構造体及びコーティング剤
WO2012011367A1 (fr) * 2010-07-23 2012-01-26 住友化学株式会社 Liquide de revêtement photocatalyseur et produit présentant une fonctionnalité photocatalytique
JP2013516638A (ja) * 2009-12-31 2013-05-13 エシロール アテルナジオナール カンパニー ジェネラーレ デ オプティック 改善された耐久性を備える一時的防曇被覆を含む光学物品
JPWO2018190408A1 (ja) * 2017-04-14 2020-03-05 Hoya株式会社 光学素子及び光学薄膜

Families Citing this family (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030039843A1 (en) * 1997-03-14 2003-02-27 Christopher Johnson Photoactive coating, coated article, and method of making same
JP3622585B2 (ja) * 1999-08-05 2005-02-23 日本板硝子株式会社 光触媒活性を有する物品
GB0017058D0 (en) * 2000-07-11 2000-08-30 Hall Vantage Limited Purification of air
FR2824846B1 (fr) 2001-05-16 2004-04-02 Saint Gobain Substrat a revetement photocatalytique
CN1401085A (zh) * 2001-06-11 2003-03-05 株式会社村上开明堂 防雾元件及其形成方法
US6884399B2 (en) 2001-07-30 2005-04-26 Carrier Corporation Modular photocatalytic air purifier
US7718144B2 (en) 2002-02-20 2010-05-18 Monzyk Bruce F Photolytic cell for providing physiological gas exchange
JP4286661B2 (ja) * 2001-08-01 2009-07-01 ブルース エフ． モンジック， 生理学的ガス交換を与えるための光分解セル
JP4075482B2 (ja) * 2001-08-08 2008-04-16 住友金属鉱山株式会社 可視光域でも触媒活性を有する光触媒
JP4736267B2 (ja) * 2001-08-08 2011-07-27 住友金属鉱山株式会社 可視光域でも触媒活性を有する光触媒
JP4116300B2 (ja) * 2002-01-31 2008-07-09 富士ゼロックス株式会社 酸化チタン光触媒薄膜および該酸化チタン光触媒薄膜の製造方法
KR100643658B1 (ko) * 2002-03-25 2006-11-10 스미토모 티타늄 가부시키가이샤 가시광형 산화티탄계 광촉매와 그 제조방법 및 응용
TWI276613B (en) 2002-04-05 2007-03-21 Murakami Corp Composite material
FR2838735B1 (fr) * 2002-04-17 2005-04-15 Saint Gobain Substrat a revetement auto-nettoyant
JP4374869B2 (ja) * 2002-05-27 2009-12-02 住友化学株式会社 セラミックス分散液の製造方法
US7521039B2 (en) * 2002-11-08 2009-04-21 Millennium Inorganic Chemicals, Inc. Photocatalytic rutile titanium dioxide
TWM249056U (en) * 2003-11-07 2004-11-01 Hon Hai Prec Ind Co Ltd Computer
EP1498176A1 (fr) * 2003-07-16 2005-01-19 Profine GmbH Revêtement photocatalytique d'un substrat
FR2861386B1 (fr) * 2003-10-23 2006-02-17 Saint Gobain Substrat, notamment substrat verrier, portant une couche a propriete photocatalytique revetue d'une couche mince protectrice.
EP1693482A4 (fr) * 2003-12-09 2008-04-30 Asahi Glass Co Ltd Film d'oxyde de titane presentant une activite photocatalytique sur l'irradiation de la lumiere visible et son procede de production
FR2864844B1 (fr) 2004-01-07 2015-01-16 Saint Gobain Dispositif d'eclairage autonettoyant
FR2868792B1 (fr) * 2004-04-13 2006-05-26 Saint Gobain Substrat photocatalytique actif sous lumiere visible
US7504156B2 (en) 2004-04-15 2009-03-17 Avery Dennison Corporation Dew resistant coatings
JP2008505841A (ja) 2004-07-12 2008-02-28 日本板硝子株式会社 低保守コーティング
WO2006031012A1 (fr) * 2004-09-15 2006-03-23 Lg Chem, Ltd. Films ou materiaux structuraux exterieurs utilisant une composition de revetement a propriete autonettoyante et procede de preparation de ladite composition
KR100614416B1 (ko) * 2004-10-11 2006-08-21 김문찬 가시광촉매 코팅액 및 제조방법
JP4894153B2 (ja) * 2005-03-23 2012-03-14 株式会社アルバック 多孔質膜の前駆体組成物及びその調製方法、多孔質膜及びその作製方法、並びに半導体装置
FR2903399B1 (fr) * 2006-07-07 2010-10-01 Saint Gobain Materiau anti-salissures et son procede d'obtention
FR2892408B1 (fr) * 2005-10-21 2008-01-11 Saint Gobain Utilisation d'un substrat anti-salissures
JP5129975B2 (ja) 2006-04-11 2013-01-30 日本板硝子株式会社 向上した低保守特性を有する光触媒コーティング
JP2007320780A (ja) * 2006-05-30 2007-12-13 Nippon Sheet Glass Co Ltd 赤外線カット膜が形成された透明物品
JP5030478B2 (ja) * 2006-06-02 2012-09-19 株式会社アルバック 多孔質膜の前駆体組成物及びその調製方法、多孔質膜及びその作製方法、並びに半導体装置
US20080011599A1 (en) 2006-07-12 2008-01-17 Brabender Dennis M Sputtering apparatus including novel target mounting and/or control
JP2008107425A (ja) * 2006-10-23 2008-05-08 Ichikoh Ind Ltd ミラーおよび光触媒活性を有する親水性複合膜
US8450594B2 (en) * 2007-07-26 2013-05-28 Guardian Industries Corp. Method of making an antireflective silica coating, resulting product and photovoltaic device comprising same
US8445774B2 (en) * 2007-07-26 2013-05-21 Guardian Industries Corp. Method of making an antireflective silica coating, resulting product, and photovoltaic device comprising same
CN101778668A (zh) * 2007-07-31 2010-07-14 开利公司 用于光催化装置寿命延长的通过形成硅酸盐的硅氧烷除去
KR101512166B1 (ko) 2007-09-14 2015-04-14 카디날 씨지 컴퍼니 관리가 용이한 코팅 기술
US20090130447A1 (en) * 2007-11-16 2009-05-21 Nth Tech Corporation Hydrophilic systems and methods thereof
US8691376B2 (en) * 2008-02-20 2014-04-08 Northrop Grumman Systems Corporation Self-decontaminating inorganic coatings containing semiconductor metal oxide nanoparticles
JP2010115635A (ja) * 2008-06-05 2010-05-27 Sumitomo Chemical Co Ltd 光触媒体分散液、その製造方法およびその用途
JP5493572B2 (ja) * 2008-08-11 2014-05-14 株式会社豊田中央研究所 光触媒体及びそれを用いた還元用触媒体
JP2015143790A (ja) * 2014-01-31 2015-08-06 住友化学株式会社 転写用光学異方性シート
CN104820255B (zh) 2014-01-31 2020-04-07 住友化学株式会社 光学各向异性片材
EP3541762B1 (fr) 2016-11-17 2022-03-02 Cardinal CG Company Technologie de revêtement à dissipation statique
KR102438146B1 (ko) * 2020-11-13 2022-08-30 한국생산기술연구원 내수코팅층을 포함하는 선택적 촉매환원반응용 촉매의 제조 방법 및 이를 이용한 내수코팅층을 포함하는 촉매환원반응용 촉매

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01232966A (ja) * 1988-03-11 1989-09-18 Matsushita Electric Ind Co Ltd 光触媒による脱臭方法
JPH01238867A (ja) * 1988-03-18 1989-09-25 Matsushita Electric Ind Co Ltd 光触媒による脱臭方法
JPH01288322A (ja) * 1988-05-13 1989-11-20 Matsushita Electric Ind Co Ltd 光触媒による脱臭方法
JPH01288321A (ja) * 1988-05-13 1989-11-20 Matsushita Electric Ind Co Ltd 光触媒による脱臭方法
JPH07124464A (ja) * 1991-10-31 1995-05-16 Pentel Kk 光触媒粉体を用いた酸化・還元方法
JPH09241037A (ja) * 1996-03-07 1997-09-16 Nissan Motor Co Ltd 防曇性被膜形成基材およびその製造方法
JPH09299808A (ja) * 1996-05-15 1997-11-25 Sumitomo Chem Co Ltd 透光性光触媒体
EP0816466A1 (fr) * 1995-03-20 1998-01-07 Toto Ltd. Procede photocatalytique pour rendre la surface de base d'un materiau ultrahydrophile, materiau de base ayant une surface ultrahydrophile et photocatalytique, et procede pour produire ce materiau
EP0820967A1 (fr) * 1996-07-26 1998-01-28 Murakami Corporation Elément antibuée
JPH10152346A (ja) * 1996-11-20 1998-06-09 Toto Ltd 光触媒性親水性部材及びその製造方法、並びに光触媒性親水性コ−ティング組成物
JPH10231146A (ja) * 1996-12-18 1998-09-02 Nippon Ita Glass Techno Res Kk 防曇防汚ガラス物品

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3207716A1 (de) 1982-03-04 1983-09-08 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von alkalihypophosphit-loesungen
JPS619264A (ja) 1984-06-25 1986-01-16 Onori Yoshizawa とうもろこしアンの製造方法
JPS62193696A (ja) * 1986-02-20 1987-08-25 Nomura Micro Sci Kk 超純水の製造法
JPH06220428A (ja) 1993-01-28 1994-08-09 Toray Ind Inc 表面改質された防曇性被膜
JPH07117202A (ja) 1993-10-21 1995-05-09 Asahi Glass Co Ltd 透明積層体及びその製造方法
JPH07225704A (ja) 1994-02-10 1995-08-22 Fuji Xerox Co Ltd ファイル管理装置
JPH0956742A (ja) 1995-06-14 1997-03-04 Toto Ltd 防曇性ゴーグル
JPH09192496A (ja) 1996-01-12 1997-07-29 Matsushita Electric Works Ltd 光触媒及びそれを備えた自己清浄品
JP3844823B2 (ja) * 1996-01-22 2006-11-15 財団法人石油産業活性化センター 光触媒、光触媒の製造方法および光触媒反応方法
JP3388993B2 (ja) 1996-04-01 2003-03-24 チタン工業株式会社 二酸化チタンを基体とする光触媒及びその製造方法
WO1998005413A1 (fr) 1996-08-05 1998-02-12 Nippon Sheet Glass Co., Ltd. Photocatalyseur et procede de preparation associe

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01232966A (ja) * 1988-03-11 1989-09-18 Matsushita Electric Ind Co Ltd 光触媒による脱臭方法
JPH01238867A (ja) * 1988-03-18 1989-09-25 Matsushita Electric Ind Co Ltd 光触媒による脱臭方法
JPH01288322A (ja) * 1988-05-13 1989-11-20 Matsushita Electric Ind Co Ltd 光触媒による脱臭方法
JPH01288321A (ja) * 1988-05-13 1989-11-20 Matsushita Electric Ind Co Ltd 光触媒による脱臭方法
JPH07124464A (ja) * 1991-10-31 1995-05-16 Pentel Kk 光触媒粉体を用いた酸化・還元方法
EP0816466A1 (fr) * 1995-03-20 1998-01-07 Toto Ltd. Procede photocatalytique pour rendre la surface de base d'un materiau ultrahydrophile, materiau de base ayant une surface ultrahydrophile et photocatalytique, et procede pour produire ce materiau
JPH09241037A (ja) * 1996-03-07 1997-09-16 Nissan Motor Co Ltd 防曇性被膜形成基材およびその製造方法
JPH09299808A (ja) * 1996-05-15 1997-11-25 Sumitomo Chem Co Ltd 透光性光触媒体
EP0820967A1 (fr) * 1996-07-26 1998-01-28 Murakami Corporation Elément antibuée
JPH10152346A (ja) * 1996-11-20 1998-06-09 Toto Ltd 光触媒性親水性部材及びその製造方法、並びに光触媒性親水性コ−ティング組成物
JPH10231146A (ja) * 1996-12-18 1998-09-02 Nippon Ita Glass Techno Res Kk 防曇防汚ガラス物品

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1066878A4 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005507974A (ja) * 2001-07-13 2005-03-24 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド 可視光応答性の光活性の被膜、被覆物品およびその製法
JP2003253157A (ja) * 2002-02-28 2003-09-10 Furukawa Co Ltd 貯蔵安定性に優れたチタニア及びチタニア系複合酸化物塗布溶液
JP2005023199A (ja) * 2003-07-02 2005-01-27 Chisso Corp 機能性超薄膜およびその形成方法
JP2007508933A (ja) * 2003-10-23 2007-04-12 サン−ゴバン グラス フランス 少なくとも１層の光触媒層と該層のヘテロエピタキシャル成長のための下地層とを備えた基材、特にガラス基材
JP2007106632A (ja) * 2005-10-14 2007-04-26 Kimoto & Co Ltd 新規ヘテロポリ酸塩、それを用いた光触媒、及び光触媒機能性部材
JP2009512573A (ja) * 2005-10-21 2009-03-26 サン−ゴバン グラス フランス 防汚性材料及びその製造方法
JP2009262071A (ja) * 2008-04-25 2009-11-12 National Univ Corp Shizuoka Univ 光触媒、光触媒機能性部材、及び水素の製造方法
JP2010005613A (ja) * 2008-05-26 2010-01-14 Asahi Kasei Chemicals Corp 複合体、機能性構造体及びコーティング剤
JP2013516638A (ja) * 2009-12-31 2013-05-13 エシロール アテルナジオナール カンパニー ジェネラーレ デ オプティック 改善された耐久性を備える一時的防曇被覆を含む光学物品
WO2012011367A1 (fr) * 2010-07-23 2012-01-26 住友化学株式会社 Liquide de revêtement photocatalyseur et produit présentant une fonctionnalité photocatalytique
JPWO2018190408A1 (ja) * 2017-04-14 2020-03-05 Hoya株式会社 光学素子及び光学薄膜
JP7091315B2 (ja) 2017-04-14 2022-06-27 Hoya株式会社 光学素子及びその製造方法

Also Published As

Publication number Publication date
DE69930399T2 (de) 2006-12-07
EP1066878A4 (fr) 2001-12-19
DE69930399D1 (de) 2006-05-11
KR20010031599A (ko) 2001-04-16
US6576344B1 (en) 2003-06-10
EP1066878B1 (fr) 2006-03-15
EP1066878A1 (fr) 2001-01-10

Similar Documents

Publication Publication Date Title
WO2000018504A1 (fr) Article photocatalyseur, article protege contre l'encrassement et le voilement, et procede de production d'un article protege contre l'encrassement et le voilement
JP3700358B2 (ja) 防曇防汚ガラス物品
CN101945964B (zh) 混杂漆料体系
US7449245B2 (en) Substrates comprising a photocatalytic TiO2 layer
JP4974459B2 (ja) 光触媒性ＴｉＯ２層を含む支持体
CN100535052C (zh) 含光催化剂的有机硅树脂组合物和具有该组合物的固化膜的涂敷制品
JP3796403B2 (ja) 光触媒性酸化物含有組成物、薄膜および複合体
JP2000289134A (ja) 親水性表面を有する物品およびその製造方法
WO2010053459A1 (fr) Préparation de sols de tio2/sio2 et leur utilisation pour le dépôt de revêtements antibuée autonettoyants
KR20150028979A (ko) 코팅 조성물 및 그의 용도
EP2644662B1 (fr) Revêtements photocatalytiques hybrides, procédé pour les appliquer sur divers substrats et utilisations des substrats ainsi revêtus
JP2004337740A (ja) 光触媒体
JP2002273233A (ja) 変性光触媒、それを用いた光触媒組成物
JP4693949B2 (ja) 光触媒層形成用塗布液、光触媒複合体および光触媒構造体
KR101760060B1 (ko) 이산화티탄 광촉매 유리코팅 조성물 및 이의 제조방법
JP4086055B2 (ja) 防曇防汚ガラス物品
CN1167760C (zh) 用于形成光催化透明亲水涂层的二氧化钛纳米涂料及其制备方法
JP2002320917A (ja) 光触媒性塗膜の製造方法、および光触媒性部材
JP2002356650A (ja) 光触媒性塗膜形成組成物およびそれを成膜した光触媒性部材
JP2001019494A (ja) 防曇ガラス物品
JP3270422B2 (ja) ガラス物品
JP4417155B2 (ja) 建築物用易洗浄性ガラスおよびその製法
JPH10130037A (ja) 防汚性と水滴付着防止性を兼ね備えた乗物用窓ガラス
JP2003105262A (ja) 光触媒性薄膜
WO1999041322A1 (fr) Matiere de revetement pour former une pellicule photocatalytique hydrophile, procede de fabrication d'une pellicule photocatalytique hydrophile, et element photocatalytique hydrophile

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): DE FR GB IT

WWE Wipo information: entry into national phase

Ref document number: 1020007004650

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 1999944879

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 09577299

Country of ref document: US

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWP Wipo information: published in national office

Ref document number: 1999944879

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020007004650

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 1020007004650

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 1999944879

Country of ref document: EP